U.S. patent application number 15/673583 was filed with the patent office on 2017-11-30 for flame retardant laser direct structuring materials.
The applicant listed for this patent is SABIC Global Technologies B.V.. Invention is credited to Yanjun Frank Li, Jiru Meng, Xiangping David Zou.
Application Number | 20170342263 15/673583 |
Document ID | / |
Family ID | 49477830 |
Filed Date | 2017-11-30 |
United States Patent
Application |
20170342263 |
Kind Code |
A1 |
Li; Yanjun Frank ; et
al. |
November 30, 2017 |
FLAME RETARDANT LASER DIRECT STRUCTURING MATERIALS
Abstract
Flame retardant thermoplastic compositions that are capable of
being used in a laser direct structuring process. The compositions
include a thermoplastic resin, a laser direct structuring additive,
and a flame retardant. The compositions offer flame retardant
characteristics while also substantially maintaining the mechanical
properties of the base thermoplastic resin, such as the impact
strength and/or HDT of the composition. The compositions can be
used in a variety of applications such as personal computers,
notebook and portable computers, cell phone and other such
communications equipment.
Inventors: |
Li; Yanjun Frank; (Shanghai,
CN) ; Meng; Jiru; (Shanghai, CN) ; Zou;
Xiangping David; (Shanghai, CN) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SABIC Global Technologies B.V. |
Bergen op Zoom |
|
NL |
|
|
Family ID: |
49477830 |
Appl. No.: |
15/673583 |
Filed: |
August 10, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13923782 |
Jun 21, 2013 |
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15673583 |
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12468474 |
May 19, 2009 |
8492464 |
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13923782 |
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61055631 |
May 23, 2008 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08K 5/0066 20130101;
C08L 71/12 20130101; C08K 2003/2251 20130101; C08K 5/5399 20130101;
C08K 3/22 20130101; C08L 71/12 20130101; C08L 69/00 20130101; C08L
71/12 20130101; C08L 25/04 20130101; C08K 3/22 20130101; C08K
5/0066 20130101; C08L 25/04 20130101; C08K 3/32 20130101; C08K 3/32
20130101; C08L 71/12 20130101; C08L 71/12 20130101; C08L 71/12
20130101; C08L 2666/24 20130101; C08K 3/32 20130101; B41M 5/24
20130101; C08K 5/0066 20130101; C08K 3/22 20130101; C08L 25/04
20130101; C08K 5/0066 20130101; C08L 47/00 20130101; B41M 5/267
20130101; C08K 5/521 20130101; C08L 69/00 20130101 |
International
Class: |
C08L 69/00 20060101
C08L069/00; C08K 3/22 20060101 C08K003/22; C08K 3/32 20060101
C08K003/32; C08L 71/12 20060101 C08L071/12; C08L 47/00 20060101
C08L047/00; C08K 5/00 20060101 C08K005/00 |
Claims
1. A thermoplastic composition, comprising: a) from 15 to 85 wt %
of a thermoplastic resin, wherein the thermoplastic resin comprises
a polyamide resin; b) from 0.1 to 30 wt % by weight of a laser
direct structuring additive; and c) 20 wt % or less of a flame
retardant; wherein a molded sample of the thermoplastic composition
is capable of achieving UL94 V0 rating at a thickness of 1.6 mm
(.+-.10%).
2. The composition of claim 1, wherein the polyamide resin
comprises polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-11,
polyamide-12, polyamide-6,10, polyamide-6,12, polyamide 6/6,6,
polyamide-6/6,12, polyamide MXD,6, polyamide-6,T, polyamide-6,I,
polyamide-6/6,T, polyamide-6/6,I, polyamide-6,6/6,T,
polyamide-6,6/6,I, polyamide-6/6,T/6,I, polyamide-6,6/6,T/6,I,
polyamide-6/12/6,T, polyamide-6,6/12/6,T, polyamide-6/12/6,I,
polyamide-6,6/12/6,I, or a combination comprising at least one of
the foregoing polyamide resins.
3. The composition of claim 1, wherein the laser direct structuring
additive is selected from a heavy metal mixture oxide spinel, a
copper salt, or a combination including at least one of the
foregoing laser direct structuring additives.
4. The composition of claim 3, wherein the laser direct structuring
additive comprises copper chromium oxide spinel or copper hydroxide
phosphate.
5. The composition of claim 1, wherein the flame retardant is
selected from a phosphorus containing flame retardant, an organic
compound containing phosphorus-nitrogen bonds, or a combination
including at least one of the foregoing flame retardants.
6. The composition of claim 1, wherein a molded sample of the
thermoplastic composition is capable of achieving UL94 V0 rating at
a thickness of 1.2 mm (.+-.10%).
7. The composition of claim 1, wherein a molded sample of the
thermoplastic composition is capable of achieving UL94 V0 rating at
a thickness of 1.0 mm (.+-.10%).
8. The composition of claim 1, wherein a molded sample of the
thermoplastic composition is capable of achieving UL94 V0 rating at
a thickness of 0.8 mm (.+-.10%).
9. The composition of claim 1, wherein the thermoplastic
composition includes from 0.1 to 15 wt % of the flame
retardant.
10. An article of manufacture comprising the composition of claim
1.
11. The article of claim 10, wherein the article is selected from a
personal computer, a notebook computer, a portable computers, a
cell phone, or a personal digital assistant.
12. A method of forming a thermoplastic composition comprising the
step of: blending in an extruder: a) from 15 to 85 wt % of a
thermoplastic resin, wherein the thermoplastic resin comprises a
polyamide resin; b) from 0.1 to 15 wt % of a laser direct
structuring additive; and c) 20 wt % or less of a flame retardant;
wherein a molded sample of the thermoplastic composition is capable
of achieving UL94 V0 rating at a thickness of 1.6 mm (.+-.10%).
13. The method of claim 12, wherein the polyamide resin comprises
polyamide-6, polyamide-6,6, polyamide-4,6, polyamide-11,
polyamide-12, polyamide-6,10, polyamide-6,12, polyamide 6/6,6,
polyamide-6/6,12, polyamide MXD,6, polyamide-6,T, polyamide-6,I,
polyamide-6/6,T, polyamide-6/6,I, polyamide-6,6/6,T,
polyamide-6,6/6,I, polyamide-6/6,T/6,I, polyamide-6,6/6,T/6,I,
polyamide-6/12/6,T, polyamide-6,6/12/6,T, polyamide-6/12/6,I,
polyamide-6,6/12/6,I, or a combination comprising at least one of
the foregoing polyamide resins.
14. The method of claim 12, wherein the laser direct structuring
additive is selected from a heavy metal mixture oxide spinel, a
copper salt, or a combination including at least one of the
foregoing laser direct structuring additives.
15. The method of claim 14, wherein the laser direct structuring
additive comprises copper chromium oxide spinel or copper hydroxide
phosphate.
16. The method of claim 12, wherein the flame retardant is selected
from a phosphorus containing flame retardant, an organic compound
containing phosphorus-nitrogen bonds, or a combination including at
least one of the foregoing flame retardants.
17. The method of claim 12, wherein a molded sample of the
thermoplastic composition is capable of achieving UL94 V0 rating at
a thickness of 1.2 mm (.+-.10%).
18. The method of claim 12, wherein a molded sample of the
thermoplastic composition is capable of achieving UL94 V0 rating at
a thickness of 1.0 mm (.+-.10%).
19. The method of claim 12, wherein a molded sample of the
thermoplastic composition is capable of achieving UL94 V0 rating at
a thickness of 0.8 mm (.+-.10%).
20. The method of claim 12, wherein the thermoplastic composition
includes from 0.1 to 15 wt % of the flame retardant.
Description
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] The present application is a divisional of U.S.
non-provisional application Ser. No. 13/923,782, filed Jun. 21,
2013, which is a continuation-in-part of U.S. Non-Provisional
patent application Ser. No. 12/468,474 filed May 19, 2009, which
claims priority to U.S. Provisional Patent Application No.
61/055,631 filed May 23, 2008, the contents of which in their
entirety are incorporated herein by.
FIELD OF THE INVENTION
[0002] The present invention relates to thermoplastic compositions
and in particular to flame retardant thermoplastic compositions
capable of being used in a laser direct structuring process. The
present invention also relates to methods of manufacturing these
compositions and articles that include these compositions.
BACKGROUND OF THE INVENTION
[0003] Electrical components may be provided as molded injection
devices (MID) with desired printed conductors, i.e., when
manufactured in MID technology, using different methods, e.g., a
masking method, in two-component injection molding with subsequent
electroplating (or electroless plating), because for some cases,
chemical plating is used for 2-component injection molding. In
contrast to conventional circuit boards made of
fiberglass-reinforced plastic or the like, MID components
manufactured in this way are three-dimensional molded parts having
an integrated printed conductor layout and possibly further
electronic or electromechanical components. The use of MID
components of this type, even if the components have only printed
conductors and are used to replace conventional wiring inside an
electrical or electronic device, saves space, allowing the relevant
device to be made smaller, and lowers the manufacturing costs by
reducing the number of assembly and contacting steps. These MID
devices have great utility in cell phones, PDAs and notebook
applications.
[0004] Stamp metal, flexible printed circuit board (FPCB) mounted
and two-shot molding methods are three existing technologies to
make an MID. However, stamping and FPCB mounted process have
limitations in the pattern geometry, and the tooling is expensive
and also altering of a RF pattern causes high-priced and
time-consuming modifications into tooling. 2-shot-molding
(two-component injection molding) processes have been used to
produce 3D-MIDs with real three-dimensional structures. The antenna
can be formed with subsequent chemical corrosion, chemical surface
activation and selective metal coating. This method involves high
initial costs and is only economically viable for large production
numbers. 2-shot-molding is also not environmentally friendly
process. All these three methods are tool-based technologies, which
have limited flexibility, long development cycles, difficult
prototype, expensive design changes, and limited
miniaturization.
[0005] Accordingly, it is becoming increasingly popular to form
MIDs using a laser direct structuring (LDS) process. In an LDS
process a computer-controlled laser beam travels over the MID to
activate the plastic surface at locations where the conductive path
is to be situated. With a laser direct structuring process, it is
possible to obtain conductive path widths of 150 microns or less.
In addition, the spacing between the conductive paths can also be
150 microns or less. As a result, MIDs formed from this process
save space and weight in the end-use applications. Another
advantage of laser direct structuring is its flexibility. If the
design of the circuit is changed, it is simply a matter of
reprogramming the computer that controls the laser.
[0006] Polycarbonate resins (PC), or polymer alloys produced by
blending one of these with a styrene resin, such as an ABS resin
(acrylonite/butadiene/styrene copolymer), are widely used in
electrical and electronic parts, personal computers, notebook and
portable computers, cell phone and other such communications
equipment. Market trends for these applications include short
development cycle, variation of design, cost reduction,
miniaturization, diversification and functionality. Internal
antenna is one of the key components for these products during the
applications. As such, it would be beneficial for MIDs to be formed
using a PC resin to enable it to be used in these types of
applications.
[0007] In addition, in the design of certain applications, such as
notebook antennas, a flame retardancy of V0 is often required. Some
of the current flame retardant additives used can adversely
mechanical properties in polycarbonate materials, such as the heat
deformation temperature (HDT) and/or impact strength. Therefore,
providing a flame retardant composition that has sufficient
mechanical properties while also being capable of being used in a
laser direct structuring process has proven difficult.
[0008] Accordingly, it would be beneficial to provide a flame
retardant thermoplastic composition that is capable of being used
in a laser direct structuring process. It would also be beneficial
to provide a polycarbonate-based flame retardant composition that
is capable of being used in a laser direct structuring process
while providing one or more benefits of using polycarbonate-based
resins. It would also be beneficial to provide a method of making a
flame retardant thermoplastic composition that is capable of being
used in a laser direct structuring process as well as providing an
article of manufacture, such as an antenna, that includes a flame
retardant thermoplastic composition that is capable of being used
in a laser direct structuring process.
BRIEF SUMMARY OF THE INVENTION
[0009] Described herein is a flame retardant thermoplastic
composition capable of being used in a laser direct structuring
process. The compositions include a thermoplastic resin, a laser
direct structuring additive and a flame retardant. The compositions
are capable of being used in a laser direct structuring process
while also providing good flame retardant characteristics and while
also maintaining beneficial mechanical properties. These
compositions can be used in a variety of products such as, for
example, electrical and electronic parts, personal computers,
notebook and portable computers, cell phone and other such
communications equipment.
[0010] Accordingly, in one embodiment, a thermoplastic composition
comprises from 15 to 85% by weight of a thermoplastic resin,
wherein the thermoplastic resin comprises a poly(arylene ether), a
poly(arylene ether)/polystyrene blend, or a combination comprising
at least one of the foregoing resins; from 0.1 to 30% by weight of
a laser direct structuring additive; and 20% or less by weight of a
flame retardant; wherein a molded sample of the thermoplastic
composition is capable of achieving UL94 V0 rating at a thickness
of 1.6 mm (.+-.10%).
[0011] In one embodiment, a thermoplastic composition comprises
from 15 to 85% by weight of a thermoplastic resin, wherein the
thermoplastic resin comprises a polyamide resin; from 0.1 to 30% by
weight of a laser direct structuring additive; and 20% or less by
weight of a flame retardant; wherein a molded sample of the
thermoplastic composition is capable of achieving UL94 V0 rating at
a thickness of 1.6 mm (.+-.10%).
[0012] In another embodiment, a method of forming a thermoplastic
composition comprises the step of: blending in an extruder: from 15
to 85% by weight of a thermoplastic resin, wherein the
thermoplastic resin comprises a poly(arylene ether), a poly(arylene
ether)/polystyrene blend, or a combination comprising at least one
of the foregoing resins; from 0.1 to 15% by weight of a laser
direct structuring additive; and 20% or less by weight of a flame
retardant; wherein a molded sample of the thermoplastic composition
is capable of achieving UL94 V0 rating at a thickness of 1.6 mm
(.+-.10%).
[0013] In another embodiment, a method of forming a thermoplastic
composition comprises the step of: blending in an extruder: from 15
to 85% by weight of a thermoplastic resin, wherein the
thermoplastic resin comprises a polyamide resin; from 0.1 to 15% by
weight of a laser direct structuring additive; and 20% or less by
weight of a flame retardant; wherein a molded sample of the
thermoplastic composition is capable of achieving UL94 V0 rating at
a thickness of 1.6 mm (.+-.10%).
[0014] These and other features and characteristics are more
particularly described below.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The present invention is more particularly described in the
following description and examples that are intended to be
illustrative only since numerous modifications and variations
therein will be apparent to those skilled in the art. As used in
the specification and in the claims, the term "comprising" can
include the embodiments "consisting of" and "consisting essentially
of." All ranges disclosed herein are inclusive of the endpoints and
are independently combinable. The endpoints of the ranges and any
values disclosed herein are not limited to the precise range or
value; they are sufficiently imprecise to include values
approximating these ranges and/or values.
[0016] As used herein, approximating language can be applied to
modify any quantitative representation that can vary without
resulting in a change in the basic function to which it is related.
Accordingly, a value modified by a term or terms, such as "about"
and "substantially," may not be limited to the precise value
specified, in some cases. In at least some instances, the
approximating language corresponds to the precision of an
instrument for measuring the value.
[0017] The present invention provides a flame retardant
thermoplastic composition capable of being used in a laser direct
structuring process. The compositions include a thermoplastic
resin, a laser direct structuring additive, and a flame retardant.
The compositions offer flame retardant characteristics while also
substantially maintaining the mechanical properties of the base
thermoplastic resin. The compositions can be used in a variety of
electrical and electronic parts, personal computers, notebook and
portable computers, cell phone and other such communications
equipment.
[0018] The flame retardant thermoplastic compositions of the
present invention, and articles made using these compositions, have
excellent physical properties as compared to prior art materials.
As has been discussed, higher levels of flame retardant have been
used in prior art compositions to achieve excellent flame retardant
characteristics. The higher levels of flame retardant have an
adverse impact on HDT and/or impact properties. The compositions of
the present invention have overcome these problems through the use
of a laser direct structuring (LDS) additive that not only enables
the compositions to be capable of being used in an LDS process, the
additive also acts as a synergist in increasing the flame
retardance of the compositions. The LDS additive permits flame
retardant characteristics to be maintained despite lower levels of
flame retardant while the lower levels of flame retardant permit
the compositions, and molded samples of these compositions, to have
higher HDT and/or impact strength. As a result, a molded sample of
the thermoplastic composition is capable of achieving UL94 V0 or V1
rating at a thickness of 1.5 mm (.+-.10%) or thinner despite lower
levels of flame retardant being used.
[0019] In one aspect, the thermoplastic compositions of the present
invention use a thermoplastic resin as the base for the
composition. Examples of thermoplastic resins that can be used in
the present invention include, but are not limited to,
polycarbonate-based resins, such as polycarbonate or a
polycarbonate/acrylonitrile-butadiene-styrene resin blend; a
poly(arylene ether) resin, such as a polyphenylene oxide resin, a
poly(arylene ether) resin/polystyrene resin blend, a polyamide
resin, or a combination including at least one of the foregoing
resins.
[0020] Accordingly, in one embodiment, the flame retardant
thermoplastic composition comprises a polycarbonate-based resin.
The polycarbonate-based resin can be selected from a polycarbonate
or a resin blend that includes a polycarbonate. Accordingly, in one
embodiment, polycarbonates can be used as the base resin in the
composition. Polycarbonates including aromatic carbonate chain
units include compositions having structural units of the formula
(I):
##STR00001##
in which the R.sup.1 groups are aromatic, aliphatic or alicyclic
radicals. Beneficially, R.sup.1 is an aromatic organic radical and,
in an alternative embodiment, a radical of the formula (II):
-A.sup.1-Y.sup.1-A.sup.2- (II)
wherein each of A.sup.1 and A.sup.2 is a monocyclic divalent aryl
radical and Y.sup.1 is a bridging radical having zero, one, or two
atoms which separate A.sup.1 from A.sup.2. In an exemplary
embodiment, one atom separates A.sup.1 from A.sup.2. Illustrative
examples of radicals of this type are --O--, --S--, --S(O)--,
--S(O.sub.2)--, --C(O)--, methylene, cyclohexyl-methylene,
2-[2,2,1]-bicycloheptylidene, ethylidene, isopropylidene,
neopentylidene, cyclohexylidene, cyclopentadecylidene,
cyclododecylidene, adamantylidene, or the like. In another
embodiment, zero atoms separate A.sup.1 from A.sup.2, with an
illustrative example being bisphenol. The bridging radical Y.sup.1
can be a hydrocarbon group or a saturated hydrocarbon group such as
methylene, cyclohexylidene or isopropylidene.
[0021] Polycarbonates can be produced by the Schotten-Bauman
interfacial reaction of the carbonate precursor with dihydroxy
compounds. Typically, an aqueous base such as sodium hydroxide,
potassium hydroxide, calcium hydroxide, or the like, is mixed with
an organic, water immiscible solvent such as benzene, toluene,
carbon disulfide, or dichloromethane, which contains the dihydroxy
compound. A phase transfer agent is generally used to facilitate
the reaction. Molecular weight regulators can be added either
singly or in admixture to the reactant mixture. Branching agents,
described forthwith can also be added singly or in admixture.
[0022] Polycarbonates can be produced by the interfacial reaction
polymer precursors such as dihydroxy compounds in which only one
atom separates A.sup.1 and A.sup.2. As used herein, the term
"dihydroxy compound" includes, for example, bisphenol compounds
having general formula (III) as follows:
##STR00002##
wherein R.sup.a and R.sup.b each independently represent hydrogen,
a halogen atom, or a monovalent hydrocarbon group; p and q are each
independently integers from 0 to 4; and X.sup.a represents one of
the groups of formula (IV):
##STR00003##
wherein R.sup.c and R.sup.d each independently represent a hydrogen
atom or a monovalent linear or cyclic hydrocarbon group, and
R.sup.e is a divalent hydrocarbon group.
[0023] Examples of the types of bisphenol compounds that can be
represented by formula (IV) include the bis(hydroxyaryl)alkane
series such as, 1,1-bis(4-hydroxyphenyl)methane,
1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)propane (or
bisphenol-A), 2,2-bis(4-hydroxyphenyl)butane,
2,2-bis(4-hydroxyphenyl)octane, 1,1-bis(4-hydroxyphenyl)propane,
1,1-bis(4-hydroxyphenyl)n-butane,
bis(4-hydroxyphenyl)phenylmethane,
2,2-bis(4-hydroxy-1-methylphenyl)propane,
1,1-bis(4-hydroxy-t-butylphenyl)propane,
2,2-bis(4-hydroxy-3-bromophenyl)propane, or the like;
bis(hydroxyaryl)cycloalkane series such as,
1,1-bis(4-hydroxyphenyl)cyclopentane,
1,1-bis(4-hydroxyphenyl)cyclohexane, or the like, or combinations
including at least one of the foregoing bisphenol compounds.
[0024] Other bisphenol compounds that can be represented by formula
(III) include those where X is --O--, --S--, --SO-- or
--SO.sub.2--. Some examples of such bisphenol compounds are
bis(hydroxyaryl)ethers such as 4,4'-dihydroxy diphenylether,
4,4'-dihydroxy-3,3'-dimethylphenyl ether, or the like; bis(hydroxy
diaryl)sulfides, such as 4,4'-dihydroxy diphenyl sulfide,
4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide, or the like;
bis(hydroxy diaryl) sulfoxides, such as, 4,4'-dihydroxy diphenyl
sulfoxides, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfoxides, or
the like; bis(hydroxy diaryl)sulfones, such as 4,4'-dihydroxy
diphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfone, or
the like; or combinations including at least one of the foregoing
bisphenol compounds.
[0025] Other bisphenol compounds that can be utilized in the
polycondensation of polycarbonate are represented by the formula
(V)
##STR00004##
wherein, R.sup.f, is a halogen atom of a hydrocarbon group having 1
to 10 carbon atoms or a halogen substituted hydrocarbon group; n is
a value from 0 to 4. When n is at least 2, R.sup.f can be the same
or different. Examples of bisphenol compounds that can be
represented by the formula (IV), are resorcinol, substituted
resorcinol compounds such as 3-methyl resorcin, 3-ethyl resorcin,
3-propyl resorcin, 3-butyl resorcin, 3-t-butyl resorcin, 3-phenyl
resorcin, 3-cumyl resorcin, 2,3,4,6-tetrafloro resorcin,
2,3,4,6-tetrabromo resorcin, or the like; catechol, hydroquinone,
substituted hydroquinones, such as 3-methyl hydroquinone, 3-ethyl
hydroquinone, 3-propyl hydroquinone, 3-butyl hydroquinone,
3-t-butyl hydroquinone, 3-phenyl hydroquinone, 3-cumyl
hydroquinone, 2,3,5,6-tetramethyl hydroquinone,
2,3,5,6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafloro
hydroquinone, 2,3,5,6-tetrabromo hydroquinone, or the like; or
combinations including at least one of the foregoing bisphenol
compounds.
[0026] Bisphenol compounds such as
2,2,2',2'-tetrahydro-3,3,3',3'-tetramethyl-1,1'-spirobi-[1H-indene]-6,6'--
diol represented by the following formula (VI) can also be
used.
##STR00005##
[0027] In one embodiment, the bisphenol compound is bisphenol
A.
[0028] Typical carbonate precursors include the carbonyl halides,
for example carbonyl chloride (phosgene), and carbonyl bromide; the
bis-haloformates, for example, the bis-haloformates of dihydric
phenols such as bisphenol A, hydroquinone, or the like, and the
bis-haloformates of glycols such as ethylene glycol and neopentyl
glycol; and the diaryl carbonates, such as diphenyl carbonate,
di(tolyl) carbonate, and di(naphthyl) carbonate. In one embodiment,
the carbonate precursor for the interfacial reaction is carbonyl
chloride.
[0029] It is also possible to employ polycarbonates resulting from
the polymerization of two or more different dihydric phenols or a
copolymer of a dihydric phenol with a glycol or with a hydroxy- or
acid-terminated polyester or with a dibasic acid or with a hydroxy
acid or with an aliphatic diacid in the event a carbonate copolymer
rather than a homopolymer is selected for use. Generally, useful
aliphatic diacids have about 2 to about 40 carbons. A beneficial
aliphatic diacid is dodecanedioic acid.
[0030] Branched polycarbonates, as well as blends of linear
polycarbonate and a branched polycarbonate can also be used in the
composition. The branched polycarbonates can be prepared by adding
a branching agent during polymerization. These branching agents can
include polyfunctional organic compounds containing at least three
functional groups, which can be hydroxyl, carboxyl, carboxylic
anhydride, haloformyl, and combinations including at least one of
the foregoing branching agents. Specific examples include
trimellitic acid, trimellitic anhydride, trimellitic trichloride,
tris-p-hydroxy phenyl ethane, isatin-bis-phenol, tris-phenol TC
(1,3,5-tris((p-hydroxyphenyl)isopropyl)benzene), tris-phenol PA
(4(4(1,1-bis(p-hydroxyphenyl)-ethyl) .alpha.,.alpha.-dimethyl
benzyl)phenol), 4-chloroformyl phthalic anhydride, trimesic acid,
benzophenone tetracarboxylic acid, or the like, or combinations
including at least one of the foregoing branching agents. The
branching agents can be added at a level of about 0.05 to about 2.0
weight percent (wt %), based upon the total weight of the
polycarbonate in a given layer.
[0031] In one embodiment, the polycarbonate can be produced by a
melt polycondensation reaction between a dihydroxy compound and a
carbonic acid diester. Examples of the carbonic acid diesters that
can be utilized to produce the polycarbonates are diphenyl
carbonate, bis(2,4-dichlorophenyl)carbonate,
bis(2,4,6-trichlorophenyl) carbonate, bis(2-cyanophenyl) carbonate,
bis(o-nitrophenyl) carbonate, ditolyl carbonate, m-cresyl
carbonate, dinaphthyl carbonate, bis(diphenyl) carbonate, bis
(methylsalicyl)carbonate, diethyl carbonate, dimethyl carbonate,
dibutyl carbonate, dicyclohexyl carbonate, or the like, or
combinations including at least one of the foregoing carbonic acid
diesters. In one embodiment, the carbonic acid diester is diphenyl
carbonate or bis (methylsalicyl)carbonate.
[0032] Beneficially, the number average molecular weight of the
polycarbonate is 3,000 to 1,000,000 grams/mole (g/mole). Within
this range, it is beneficial to have a number average molecular
weight of greater than or equal to 10,000 in one embodiment,
greater than or equal to 20,000 in another embodiment, and greater
than or equal to 25,000 g/mole in yet another embodiment. Also
beneficial is a number average molecular weight of less than or
equal to 100,000 in one embodiment, less than or equal to 75,000 in
an alternative embodiment, less than or equal to 50,000 in still
another alternative embodiment, and less than or equal to 35, 000
g/mole in yet another alternative embodiment.
[0033] "Polycarbonates" includes homopolycarbonates (wherein each
R.sup.1 in the polymer is the same), copolymers comprising
different R.sup.1 moieties in the carbonate ("copolycarbonates"),
copolymers comprising carbonate units and other types of polymer
units, such as ester units, and combinations comprising at least
one of homopolycarbonates and/or copolycarbonates.
[0034] In another embodiment, the polycarbonate-based resin used in
the thermoplastic composition includes a polycarbonate resin blend,
such that a polycarbonate is blended with another resin. In one
embodiment, the polycarbonate-based resin includes a blend of a
polycarbonate with a polystyrene polymer. Examples include
polycarbonate/acrylonitrile-butadiene-styrene resin blends.
[0035] The term "polystyrene" as used herein includes polymers
prepared by bulk, suspension and emulsion polymerization, which
contain at least 25% by weight of polymer precursors having
structural units derived from a monomer of the formula (VII):
##STR00006##
wherein R.sup.5 is hydrogen, lower alkyl or halogen; Z.sup.1 is
vinyl, halogen or lower alkyl; and p is from 0 to about 5. These
organic polymers include homopolymers of styrene, chlorostyrene and
vinyltoluene, random copolymers of styrene with one or more
monomers illustrated by acrylonitrile, butadiene, alpha
-methylstyrene, ethylvinylbenzene, divinylbenzene and maleic
anhydride, and rubber-modified polystyrenes including blends and
grafts, wherein the rubber is a polybutadiene or a rubbery
copolymer of about 98 to about 70 wt % styrene and about 2 to about
30 wt % diene monomer.
[0036] Polystyrenes are miscible with polyphenylene ether in all
proportions, and any such blend can contain polystyrene in amounts
of about 5 to about 95 wt % and most often about 25 to about 75 wt
%, based on the total weight of the polymers.
[0037] In another embodiment, the thermoplastic resin comprises a
poly(arylene ether) resin. Suitable poly(arylene ether) resins
include those comprising repeating structural units having the
formula
##STR00007##
wherein each occurrence of Z.sup.1 is independently halogen,
unsubstituted or substituted C.sub.1-C.sub.12 hydrocarbyl provided
that the hydrocarbyl group is not tertiary hydrocarbyl,
C.sub.1-C.sub.12 hydrocarbylthio, C.sub.1-C.sub.12 hydrocarbyloxy,
or C.sub.2-C.sub.12 halohydrocarbyloxy wherein at least two carbon
atoms separate the halogen and oxygen atoms; and each occurrence of
Z.sup.2 is independently hydrogen, halogen, unsubstituted or
substituted C.sub.1-C.sub.12 hydrocarbyl provided that the
hydrocarbyl group is not tertiary hydrocarbyl, C.sub.1-C.sub.12
hydrocarbylthio, C.sub.1-C.sub.12 hydrocarbyloxy, or
C.sub.2-C.sub.12 halohydrocarbyloxy wherein at least two carbon
atoms separate the halogen and oxygen atoms.
[0038] As used herein, the term "hydrocarbyl", whether used by
itself, or as a prefix, suffix, or fragment of another term, refers
to a residue that contains only carbon and hydrogen. The residue
can be aliphatic or aromatic, straight-chain, cyclic, bicyclic,
branched, saturated, or unsaturated. It can also contain
combinations of aliphatic, aromatic, straight chain, cyclic,
bicyclic, branched, saturated, and unsaturated hydrocarbon
moieties. However, when the hydrocarbyl residue is described as
substituted, it can, optionally, contain heteroatoms over and above
the carbon and hydrogen members of the substituent residue. Thus,
when specifically described as substituted, the hydrocarbyl residue
can also contain one or more carbonyl groups, amino groups,
hydroxyl groups, or the like, or it can contain heteroatoms within
the backbone of the hydrocarbyl residue. As one example, Z.sup.1
can be a di-n-butylaminomethyl group formed by reaction of a
3,5-dimethyl-1,4-phenyl group with the di-n-butylamine component of
an oxidative polymerization catalyst.
[0039] The poly(arylene ether) can comprise molecules having
aminoalkyl-containing end group(s), typically located in an ortho
position to the hydroxy group. Also frequently present are
tetramethyl diphenylquinone (TMDQ) end groups, typically obtained
from reaction mixtures in which tetramethyl diphenylquinone
by-product is present. The poly(phenylene ether) can be in the form
of a homopolymer, a copolymer, a graft copolymer, an ionomer, or a
block copolymer, as well as combinations thereof.
[0040] In some embodiments, the poly(arylene ether) comprises
2,6-dimethyl-1,4-phenylene ether repeating units,
2,3,6-trimethyl-1,4-phenylene ether units, or a combination
thereof. In some embodiments, the poly(arylene ether) is a
poly(2,6-dimethyl-1,4-phenylene ether), also known as polyphenylene
oxide (PPO).
[0041] The poly(arylene ether) can have a number average molecular
weight of 3,000 to 40,000 grams per mole (g/mol) and a weight
average molecular weight of 5,000 to 80,000 g/mol, as determined by
gel permeation chromatography using monodisperse polystyrene
standards, a styrene divinyl benzene gel at 40.degree. C. and
samples having a concentration of 1 milligram per milliliter of
chloroform. The poly(arylene ether) or combination of poly(arylene
ether)s has an intrinsic viscosity of 0.2 to 1 deciliter per gram
measured at 25.degree. C. in chloroform. Within this range, the
poly(arylene ether) intrinsic viscosity can be 0.25 to 0.8
deciliter per gram, more specifically 0.25 to 0.7 deciliter per
gram, even more specifically 0.3 to 0.65 deciliter per gram, yet
more specifically 0.35 to 0.6 deciliter per gram.
[0042] The poly(arylene ether) resin can be blended with another
resin. In one embodiment, the thermoplastic resin is a blend of a
poly(arylene ether) resin with a polystyrene polymer, for example,
a poly(2,6-dimethyl-1,4-phenylene ether)/polystyrene resin blend.
Polystyrenes are miscible with polyphenylene ether in all
proportions, and any such blend can contain polystyrene in amounts
of about 5 to about 95 wt % and most often about 25 to about 75 wt
%, based on the total weight of the polymers.
[0043] Examples of the polystyrene which can be blended with the
poly(arylene ether) resin include homopolystyrenes, rubber-modified
polystyrenes, unhydrogenated block copolymers of an alkenyl
aromatic monomer and a conjugated diene, hydrogenated block
copolymers of an alkenyl aromatic monomer and a conjugated diene,
and combinations comprising at least one of the foregoing
polystyrene resins.
[0044] In other embodiments, the thermoplastic resin comprises a
polyamide resin. Polyamide resins, also known as nylons, are
characterized by the presence of an amide group (--C(O)NH--).
Examples of polyamide resins include polyamide-6, polyamide-6,6,
polyamide-4,6, polyamide-11, polyamide-12, polyamide-6,10,
polyamide-6,12, polyamide 6/6,6, polyamide-6/6,12, polyamide MXD,6
(where MXD is m-xylylene diamine), polyamide-6,T, polyamide-6,I,
polyamide-6/6,T, polyamide-6/6,I, polyamide-6,6/6,T,
polyamide-6,6/6,I, polyamide-6/6,T/6,I, polyamide-6,6/6,T/6,I,
polyamide-6/12/6,T, polyamide-6,6/12/6,T, polyamide-6/12/6,I,
polyamide-6,6/12/6,I, and a combination thereof. In some
embodiments, the polyamide comprises polyamide-6, polyamide-6,6, or
a combination thereof.
[0045] Polyamides can be prepared by a number of known processes,
and polyamides are commercially available from a variety of
sources.
[0046] The amount of the thermoplastic resin used in the
thermoplastic compositions of the present invention can be based on
the selected properties of the thermoplastic compositions as well
as molded articles made from these compositions. Other factors
include the selected impact strength of the thermoplastic
composition, the selected HDT of the thermoplastic composition, the
amount and/or type of flame retardant used, the amount and/or type
of the LDS additive used, or a combination including at least one
of the foregoing factors. In one embodiment, the thermoplastic
resin is present in amounts of from 15 to 85 wt. %. In another
embodiment, the thermoplastic resin is present in amounts from 20
to 80 wt. %. In still another embodiment, the thermoplastic resin
is present in amounts from 25 to 70 wt. %.
[0047] In addition to the thermoplastic resin, the compositions of
the present invention also include a laser direct structuring (LDS)
additive. The LDS additive is selected to enable the composition to
be used in a laser direct structuring process. In an LDS process, a
laser beam exposes the LDS additive to place it at the surface of
the thermoplastic composition and to activate metal atoms from the
LDS additive. As such, the LDS additive is selected such that, upon
exposed to a laser beam, metal atoms are activated and exposed and
in areas not exposed by the laser beam, no metal atoms are exposed.
In addition, the LDS additive is selected such that, after being
exposed to laser beam, the etching area is capable of being plated
to form conductive structure. As used herein "capable of being
plated" refers to a material wherein a substantially uniform metal
plating layer can be plated on laser-etched area and show a wide
window for laser parameters.
[0048] In addition to enabling the composition to be used in a
laser direct structuring process, the LDS additive used in the
present invention is also selected to enhance the flame retardant
characteristics of the composition. Many known flame retardants
adversely affect the heat deformation temperature (HDT) and/or
other mechanical properties of the composition (such as impact
strength). As such, many flame retardant materials have less
utility in structural type applications. However, by using an LDS
additive that also enhances the flame retardant characteristics of
the composition, less flame retardant is needed to achieve a
selected flame retardancy, thereby enabling the compositions of the
present invention to have HDTs and/or other mechanical properties
that are similar to a polycarbonate-based resin having no flame
retardant.
[0049] Examples of LDS additives useful in the present invention
include, but are not limited to, a heavy metal mixture oxide
spinel, such as copper chromium oxide spinel; a copper salt, such
as copper hydroxide phosphate; copper phosphate, copper sulfate,
cuprous thiocyanate; or a combination including at least one of the
foregoing LDS additives.
[0050] In one embodiment, the LDS additive is a heavy metal mixture
oxide spinel, such as copper chromium. The use of the heavy metal
mixture oxide spinel enables the composition to be used in a laser
direct structuring process while also enhancing the flame retardant
characteristics of the composition such that lower amounts of a
flame retardant are used, thereby improving the HDT and/or
mechanical properties of the compositions. In one embodiment, the
LDS additive is present in amounts of from 0.1 to 30 wt. %. In
another embodiment, the LDS additive is present in amounts from 0.2
to 15 wt. %. In still another embodiment, the LDS additive is
present in amounts from 0.5 to 8 wt. %.
[0051] As discussed, the LDS additive is selected such that, after
activating with a laser, the conductive path can be formed by
followed a standard electroless plating process. When the LDS
additive is exposed to the laser, elemental metal is released. The
laser draws the circuit pattern onto the part and leaves behind a
roughened surface containing embedded metal particles. These
particles act as nuclei for the crystal growth during a subsequent
plating process, such as a copper plating process. Other
electroless plating processes that can be used include, but are not
limited to, gold plating, nickel plating, silver plating, zinc
plating, tin plating or the like.
[0052] In addition to the foregoing components, the thermoplastic
compositions of the present invention further include a flame
retardant. In one embodiment, the flame retardant is a phosphorus
containing flame retardant, for example an organic phosphate and/or
an organic compound containing phosphorus-nitrogen bonds.
[0053] One type of organic phosphate is an aromatic phosphate of
the formula (GO).sub.3P.dbd.O, wherein each G is independently an
alkyl, cycloalkyl, aryl, alkaryl, or aralkyl group, provided that
at least one G is an aromatic group. Two of the G groups can be
joined together to provide a cyclic group, for example, diphenyl
pentaerythritol diphosphate, which is described by Axelrod in U.S.
Pat. No. 4,154,775. Other suitable aromatic phosphates can be, for
example, phenyl bis(dodecyl) phosphate, phenyl bis(neopentyl)
phosphate, phenyl bis(3,5,5'-trimethylhexyl) phosphate, ethyl
diphenyl phosphate, 2-ethylhexyl di(p-tolyl) phosphate,
bis(2-ethylhexyl) p-tolyl phosphate, tritolyl phosphate,
bis(2-ethylhexyl) phenyl phosphate, tri(nonylphenyl) phosphate,
bis(dodecyl) p-tolyl phosphate, dibutyl phenyl phosphate,
2-chloroethyl diphenyl phosphate, p-tolyl
bis(2,5,5'-trimethylhexyl) phosphate, 2-ethylhexyl diphenyl
phosphate, or the like. A specific aromatic phosphate is one in
which each G is aromatic, for example, triphenyl phosphate,
tricresyl phosphate, isopropylated triphenyl phosphate, and the
like.
[0054] Di- or polyfunctional aromatic phosphorus-containing
compounds are also useful, for example, compounds of the formulas
below:
##STR00008##
wherein each G.sup.1 is independently a hydrocarbon having 1 to 30
carbon atoms; each G.sup.2 is independently a hydrocarbon or
hydrocarbonoxy having 1 to 30 carbon atoms; each X is independently
a bromine or chlorine; m 0 to 4, and n is 1 to 30. Examples of
suitable di- or polyfunctional aromatic phosphorus-containing
compounds include resorcinol tetraphenyl diphosphate (RDP), the
bis(diphenyl) phosphate of hydroquinone and the bis(diphenyl)
phosphate of bisphenol-A, respectively, their oligomeric and
polymeric counterparts, and the like. Methods for the preparation
of the aforementioned di- or polyfunctional aromatic compounds are
described in British Patent No. 2,043,083.
[0055] The amount of flame retardant added to the thermoplastic
compositions of the present invention can be based on the amount
and type of thermoplastic resin used, the amount and/or type of LDS
additive used, and/or the amount and presence of other components
in the thermoplastic compositions. However, as discussed, the use
of certain flame-retardants can adversely affect certain properties
of the thermoplastic compositions such as impact strength and/or
the HDT. Accordingly, in the present invention, the amount of flame
retardant in the thermoplastic composition is sufficient to impart
flame retardant characteristics while still maintaining a selected
impact strength and/or HDT. In one embodiment, the flame retardant
is added in amounts up to 20 wt. %. In another embodiment, the
flame retardant is added in amounts up to 15 wt. %. In still
another embodiment, the flame retardant is added in amounts up to
10 wt. %.
[0056] The thermoplastic compositions of the present invention are
essentially free of chlorine and bromine, particularly chlorine and
bromine flame-retardants. "Essentially free of chlorine and
bromine" as used herein refers to materials produced without the
intentional addition of chlorine, bromine, and/or chlorine or
bromine containing materials. It is understood however that in
facilities that process multiple products a certain amount of cross
contamination can occur resulting in bromine and/or chlorine levels
typically on the parts per million by weight scale. With this
understanding it can be readily appreciated that essentially free
of bromine and chlorine can be defined as having a bromine and/or
chlorine content of less than or equal to 100 parts per million by
weight (ppm), less than or equal to 75 ppm, or less than or equal
to 50 ppm. When this definition is applied to the fire retardant it
is based on the total weight of the fire retardant. When this
definition is applied to the thermoplastic composition it is based
on the total weight of polycarbonate, LDS additive and the flame
retardant.
[0057] Optionally, inorganic flame retardants can also be used, for
example sulfonate salts such as potassium perfluorobutane sulfonate
(Rimar salt) and potassium diphenylsulfone sulfonate; salts formed
by reacting for example an alkali metal or alkaline earth metal
(preferably lithium, sodium, potassium, magnesium, calcium and
barium salts) and an inorganic acid complex salt, for example, an
oxo-anion, such as alkali metal and alkaline-earth metal salts of
carbonic acid, such as Na.sub.2CO.sub.3, K.sub.2CO.sub.3,
MgCO.sub.3, CaCO.sub.3, BaCO.sub.3, and BaCO.sub.3 or fluoro-anion
complex such as Li.sub.3AlF.sub.6, BaSiF.sub.6, KBF.sub.4,
K.sub.3AlF.sub.6, KAlF.sub.4, K.sub.2SiF.sub.6, and/or Na.sub.3AlF6
or the like. When present, inorganic flame retardant salts are
generally present in amounts of from 0.01 to 1.0 parts by weight,
more specifically from 0.05 to 0.5 parts by weight, based on 100
parts by weight of polycarbonate-based resin, the LDS additive, and
the flame retardant.
[0058] Anti-drip agents can also be included in the composition,
and include, for example fluoropolymers, such as a fibril forming
or non-fibril forming fluoropolymer such as fibril forming
polytetrafluoroethylene (PTFE) or non-fibril forming
polytetrafluoroethylene, or the like; encapsulated fluoropolymers,
i.e., a fluoropolymer encapsulated in a polymer as the anti-drip
agent, such as a styrene-acrylonitrile copolymer encapsulated PTFE
(TSAN) or the like, or combinations including at least one of the
foregoing antidrip agents. An encapsulated fluoropolymer can be
made by polymerizing the polymer in the presence of the
fluoropolymer. TSAN can be made by copolymerizing styrene and
acrylonitrile in the presence of an aqueous dispersion of PTFE.
TSAN can provide significant advantages over PTFE, in that TSAN can
be more readily dispersed in the composition. TSAN can, for
example, include 50 wt. % PTFE and 50 wt. % styrene-acrylonitrile
copolymer, based on the total weight of the encapsulated
fluoropolymer. The styrene-acrylonitrile copolymer can, for
example, be 75 wt. % styrene and 25 wt. % acrylonitrile based on
the total weight of the copolymer. Alternatively, the fluoropolymer
can be pre-blended in some manner with a second polymer, such as
for, example, an aromatic polycarbonate resin or a
styrene-acrylonitrile resin as in, for example, U.S. Pat. Nos.
5,521,230 and 4,579,906 to form an agglomerated material for use as
an anti-drip agent. Either method can be used to produce an
encapsulated fluoropolymer. Antidrip agents are generally used in
amounts of from 0.1 to 1.4 parts by weight, based on 100 parts by
weight of based on 100 parts by weight of the total composition,
exclusive of any filler.
[0059] In addition to the thermoplastic resin, the LDS additive and
the flame retardant, the thermoplastic compositions of the present
invention can include various additives ordinarily incorporated in
resin compositions of this type. Mixtures of additives can be used.
Such additives can be mixed at a suitable time during the mixing of
the components for forming the composition. The one or more
additives are included in the thermoplastic compositions to impart
one or more selected characteristics to the thermoplastic
compositions and any molded article made therefrom. Examples of
additives that can be included in the present invention include,
but are not limited to, heat stabilizers, process stabilizers,
antioxidants, light stabilizers, plasticizers, antistatic agents,
mold releasing agents, UV absorbers, lubricants, pigments, dyes,
colorants, flow promoters, impact modifiers or a combination of one
or more of the foregoing additives.
[0060] Suitable heat stabilizers include, for example, organo
phosphites such as triphenyl phosphite,
tris-(2,6-dimethylphenyl)phosphite, tris-(mixed mono-and
di-nonylphenyl)phosphite or the like; phosphonates such as
dimethylbenzene phosphonate or the like, phosphates such as
trimethyl phosphate, or the like, or combinations including at
least one of the foregoing heat stabilizers. Heat stabilizers are
generally used in amounts of from 0.01 to 0.5 parts by weight based
on 100 parts by weight of the total composition, excluding any
filler.
[0061] Suitable antioxidants include, for example, organophosphites
such as tris(nonyl phenyl)phosphite,
tris(2,4-di-t-butylphenyl)phosphite,
bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, distearyl
pentaerythritol diphosphite or the like; alkylated monophenols or
polyphenols; alkylated reaction products of polyphenols with
dienes, such as
tetrakis[methylene(3,5-di-tert-butyl-4-hydroxyhydrocinnamate)]
methane, or the like; butylated reaction products of para-cresol or
dicyclopentadiene; alkylated hydroquinones; hydroxylated
thiodiphenyl ethers; alkylidene-bisphenols; benzyl compounds;
esters of beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid
with monohydric or polyhydric alcohols; esters of
beta-(5-tert-butyl-4-hydroxy-3-methylphenyl)-propionic acid with
monohydric or polyhydric alcohols; esters of thioalkyl or thioaryl
compounds such as distearylthiopropionate, dilaurylthiopropionate,
ditridecylthiodipropionate,
octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,
pentaerythrityl-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate
or the like; amides of
beta-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionic acid or the
like, or combinations including at least one of the foregoing
antioxidants. Antioxidants are generally used in amounts of from
0.01 to 0.5 parts by weight, based on 100 parts by weight of the
total composition, excluding any filler.
[0062] Suitable light stabilizers include, for example,
benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole,
2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and
2-hydroxy-4-n-octoxy benzophenone or the like or combinations
including at least one of the foregoing light stabilizers. Light
stabilizers are generally used in amounts of from 0.1 to 1.0 parts
by weight, based on 100 parts by weight of the total composition,
excluding any filler.
[0063] Suitable plasticizers include, for example, phthalic acid
esters such as dioctyl-4,5-epoxy-hexahydrophthalate,
tris-(octoxycarbonylethyl)isocyanurate, tristearin, epoxidized
soybean oil or the like, or combinations including at least one of
the foregoing plasticizers. Plasticizers are generally used in
amounts of from 0.5 to 3.0 parts by weight, based on 100 parts by
weight of the total composition, excluding any filler.
[0064] Suitable antistatic agents include, for example, glycerol
monostearate, sodium stearyl sulfonate, sodium
dodecylbenzenesulfonate or the like, or combinations of the
foregoing antistatic agents. In one embodiment, carbon fibers,
carbon nanofibers, carbon nanotubes, carbon black, or any
combination of the foregoing can be used in a polymeric resin
containing chemical antistatic agents to render the composition
electrostatically dissipative.
[0065] Suitable mold releasing agents include for example, metal
stearate, stearyl stearate, pentaerythritol tetrastearate, beeswax,
montan wax, paraffin wax, or the like, or combinations including at
least one of the foregoing mold release agents. Mold releasing
agents are generally used in amounts of from 0.1 to 1.0 parts by
weight, based on 100 parts by weight of the total composition,
excluding any filler.
[0066] Suitable UV absorbers include for example,
hydroxybenzophenones; hydroxybenzotriazoles; hydroxybenzotriazines;
cyanoacrylates; oxanilides; benzoxazinones;
2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol(CYASORB.TM.
5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB.TM. 531);
2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)-phenol
(CYASORB.TM. 1164);
2,2'-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one) (CYASORB.TM.
UV-3638);
1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenyl-
acryloyl)oxy]methyl]propane (UVINUL.TM. 3030); 2,2'-(1,4-phenylene)
bis(4H-3,1-benzoxazin-4-one);
1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenyl-
acryloyl)oxy]methyl]propane; nano-size inorganic materials such as
titanium oxide, cerium oxide, and zinc oxide, all with particle
size less than 100 nanometers; or the like, or combinations
including at least one of the foregoing UV absorbers. UV absorbers
are generally used in amounts of from 0.01 to 3.0 parts by weight,
based on 100 parts by weight based on 100 parts by weight of the
total composition, excluding any filler.
[0067] Suitable lubricants include for example, fatty acid esters
such as alkyl stearyl esters, e.g., methyl stearate or the like;
mixtures of methyl stearate and hydrophilic and hydrophobic
surfactants including polyethylene glycol polymers, polypropylene
glycol polymers, and copolymers thereof e.g., methyl stearate and
polyethylene-polypropylene glycol copolymers in a suitable solvent;
or combinations including at least one of the foregoing lubricants.
Lubricants are generally used in amounts of from 0.1 to 5 parts by
weight, based on 100 parts by weight of the total composition,
excluding any filler.
[0068] Suitable pigments include for example, inorganic pigments
such as metal oxides and mixed metal oxides such as zinc oxide,
titanium dioxides, iron oxides or the like; sulfides such as zinc
sulfides, or the like; aluminates; sodium sulfo-silicates; sulfates
and chromates; carbon blacks; zinc ferrites; ultramarine blue;
Pigment Brown 24; Pigment Red 101; Pigment Yellow 119; organic
pigments such as azos, di-azos, quinacridones, perylenes,
naphthalene tetracarboxylic acids, flavanthrones, isoindolinones,
tetrachloroisoindolinones, anthraquinones, anthanthrones,
dioxazines, phthalocyanines, and azo lakes; Pigment Blue 60,
Pigment Red 122, Pigment Red 149, Pigment Red 177, Pigment Red 179,
Pigment Red 202, Pigment Violet 29, Pigment Blue 15, Pigment Green
7, Pigment Yellow 147 and Pigment Yellow 150, or combinations
including at least one of the foregoing pigments. Pigments are
generally used in amounts of from 1 to 10 parts by weight, based on
100 parts by weight based on 100 parts by weight of the total
composition, excluding any filler.
[0069] Suitable dyes include, for example, organic dyes such as
coumarin 460 (blue), coumarin 6 (green), nile red or the like;
lanthanide complexes; hydrocarbon and substituted hydrocarbon dyes;
polycyclic aromatic hydrocarbons; scintillation dyes (preferably
oxazoles and oxadiazoles); aryl- or heteroaryl-substituted poly
(2-8 olefins); carbocyanine dyes; phthalocyanine dyes and pigments;
oxazine dyes; carbostyryl dyes; porphyrin dyes; acridine dyes;
anthraquinone dyes; arylmethane dyes; azo dyes; diazonium dyes;
nitro dyes; quinone imine dyes; tetrazolium dyes; thiazole dyes;
perylene dyes, perinone dyes; bis-benzoxazolylthiophene (BBOT); and
xanthene dyes; fluorophores such as anti-stokes shift dyes which
absorb in the near infrared wavelength and emit in the visible
wavelength, or the like; luminescent dyes such as
5-amino-9-diethyliminobenzo(a)phenoxazonium perchlorate;
7-amino-4-methylcarbostyryl; 7-amino-4-methylcoumarin;
3-(2'-benzimidazolyl)-7-N,N-diethylaminocoumarin;
3-(2'-benzothiazolyl)-7-diethylaminocoumarin;
2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole;
2-(4-biphenyl)-6-phenylbenzoxazole-1,3;
2,5-Bis-(4-biphenylyl)-1,3,4-oxadiazole;
2,5-bis-(4-biphenylyl)-oxazole;
4,4'-bis-(2-butyloctyloxy)-p-quaterphenyl;
p-bis(o-methylstyryl)-benzene; 5,9-diaminobenzo(a)phenoxazonium
perchlorate;
4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran;
1,1'-diethyl-2,2'-carbocyanine iodide;
3,3'-diethyl-4,4',5,5'-dibenzothiatricarbocyanine iodide;
7-diethylamino-4-methylcoumarin;
7-diethylamino-4-trifluoromethylcoumarin;
2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl;
7-ethylamino-6-methyl-4-trifluoromethylcoumarin;
7-ethylamino-4-trifluoromethylcoumarin; nile red; rhodamine 700;
oxazine 750; rhodamine 800; IR 125; IR 144; IR 140; IR 132; IR 26;
IR5; diphenylhexatriene; diphenylbutadiene; tetraphenylbutadiene;
naphthalene; anthracene; 9,10-diphenylanthracene; pyrene; chrysene;
rubrene; coronene; phenanthrene or the like, or combinations
including at least one of the foregoing dyes. Dyes are generally
used in amounts of from 0.1 to 5 parts by weight, based on 100
parts by weight of the total composition, excluding any filler.
[0070] Suitable colorants include, for example titanium dioxide,
anthraquinones, perylenes, perinones, indanthrones, quinacridones,
xanthenes, oxazines, oxazolines, thioxanthenes, indigoids,
thioindigoids, naphthalimides, cyanines, xanthenes, methines,
lactones, coumarins, bis-benzoxazolylthiophene (BBOT),
napthalenetetracarboxylic derivatives, monoazo and disazo pigments,
triarylmethanes, aminoketones, bis(styryl)biphenyl derivatives, and
the like, as well as combinations including at least one of the
foregoing colorants. Colorants are generally used in amounts of
from 0.1 to 5 parts by weight, based on 100 parts by weight of the
total composition, excluding any filler.
[0071] Suitable blowing agents include for example, low boiling
halohydrocarbons and those that generate carbon dioxide; blowing
agents that are solid at room temperature and when heated to
temperatures higher than their decomposition temperature, generate
gases such as nitrogen, carbon dioxide, ammonia gas, such as
azodicarbonamide, metal salts of azodicarbonamide, 4,4'
oxybis(benzenesulfonylhydrazide), sodium bicarbonate, ammonium
carbonate, or the like, or combinations including at least one of
the foregoing blowing agents. Blowing agents are generally used in
amounts of from 1 to 20 parts by weight, based on 100 parts by
weight of the total composition, excluding any filler.
[0072] Additionally, materials to improve flow and other properties
can be added to the composition, such as low molecular weight
hydrocarbon resins. Particularly useful classes of low molecular
weight hydrocarbon resins are those derived from petroleum C.sub.5
to C.sub.9 feedstock that are derived from unsaturated C.sub.5 to
C.sub.9 monomers obtained from petroleum cracking. Non-limiting
examples include olefins, e.g. pentenes, hexenes, heptenes and the
like; diolefins, e.g. pentadienes, hexadienes and the like; cyclic
olefins and diolefins, e.g. cyclopentene, cyclopentadiene,
cyclohexene, cyclohexadiene, methyl cyclopentadiene and the like;
cyclic diolefin dienes, e.g., dicyclopentadiene,
methylcyclopentadiene dimer and the like; and aromatic
hydrocarbons, e.g. vinyltoluenes, indenes, methylindenes and the
like. The resins can additionally be partially or fully
hydrogenated.
[0073] Lastly, the compositions of the present invention can, in
alternative embodiments, include one or more fillers. These fillers
can be selected to impart additional impact strength and/or provide
additional characteristics that can be based on the final selected
characteristics of the thermoplastic compositions. Suitable fillers
or reinforcing agents include, for example, TiO.sub.2; fibers, such
as asbestos, carbon fibers, or the like; silicates and silica
powders, such as aluminum silicate (mullite), synthetic calcium
silicate, zirconium silicate, fused silica, crystalline silica
graphite, natural silica sand, or the like; boron powders such as
boron-nitride powder, boron-silicate powders, or the like; alumina;
magnesium oxide (magnesia); calcium sulfate (as its anhydride,
dihydrate or trihydrate); calcium carbonates such as chalk,
limestone, marble, synthetic precipitated calcium carbonates, or
the like; talc, including fibrous, modular, needle shaped, lamellar
talc, or the like; wollastonite; surface-treated wollastonite;
glass spheres such as hollow and solid glass spheres, silicate
spheres, cenospheres, aluminosilicate (armospheres),or the like;
kaolin, including hard kaolin, soft kaolin, calcined kaolin, kaolin
including various coatings known in the art to facilitate
compatibility with the polymeric matrix resin, or the like; single
crystal fibers or "whiskers" such as silicon carbide, alumina,
boron carbide, iron, nickel, copper, or the like; glass fibers,
(including continuous and chopped fibers), such as E, A, C, ECR, R,
S, D, and NE glasses and quartz, or the like; sulfides such as
molybdenum sulfide, zinc sulfide or the like; barium compounds such
as barium titanate, barium ferrite, barium sulfate, heavy spar, or
the like; metals and metal oxides such as particulate or fibrous
aluminum, bronze, zinc, copper and nickel or the like; flaked
fillers such as glass flakes, flaked silicon carbide, aluminum
diboride, aluminum flakes, steel flakes or the like; fibrous
fillers, for example short inorganic fibers such as those derived
from blends including at least one of aluminum silicates, aluminum
oxides, magnesium oxides, and calcium sulfate hemihydrate or the
like; natural fillers and reinforcements, such as wood flour
obtained by pulverizing wood, fibrous products such as cellulose,
cotton, sisal, jute, starch, cork flour, lignin, ground nut shells,
corn, rice grain husks or the like; reinforcing organic fibrous
fillers formed from organic polymers capable of forming fibers such
as poly(ether ketone), polyimide, polybenzoxazole, poly(phenylene
sulfide), polyesters, polyethylene, aromatic polyamides, aromatic
polyimides, polyetherimides, polytetrafluoroethylene, acrylic
resins, poly(vinyl alcohol) or the like; as well as additional
fillers and reinforcing agents such as mica, clay, feldspar, flue
dust, fillite, quartz, quartzite, perlite, tripoli, diatomaceous
earth, carbon black, or the like, or combinations including at
least one of the foregoing fillers or reinforcing agents.
[0074] The fillers and reinforcing agents can be surface treated
with silanes to improve adhesion and dispersion with the polymeric
matrix resin. In addition, the reinforcing fillers can be provided
in the form of monofilament or multifilament fibers and can be used
either alone or in combination with other types of fiber, through,
for example, co-weaving or core/sheath, side-by-side, orange-type
or matrix and fibril constructions, or by other methods known to
one skilled in the art of fiber manufacture. Suitable cowoven
structures include, for example, aromatic polyimide fiberglass
fiber or the like. Fibrous fillers can be supplied in the form of,
for example, rovings, woven fibrous reinforcements, such as 0-90
degree fabrics or the like; non-woven fibrous reinforcements such
as continuous strand mat, chopped strand mat, tissues, papers and
felts or the like; or three-dimensional reinforcements such as
braids. Fillers are generally used in amounts of from 1 to 50 parts
by weight, based on 100 parts by weight of the total
composition.
[0075] In another embodiment, the thermoplastic compositions are of
particular utility in the manufacture flame retardant articles that
pass the UL94 vertical burn tests, in particular the UL94 V0
standard, which is more stringent than the UL94 V1 standard. Thin
articles present a particular challenge in the UL 94 tests, because
compositions suitable for the manufacture of thin articles tend to
have a higher flow.
[0076] Flame retardance of samples made from the thermoplastic
compositions of the present invention is excellent. Using this
standard, the thermoplastic compositions are formed into a molded
article having a given thickness. In one embodiment, a molded
sample of the thermoplastic composition is capable of achieving
UL94 V0 rating at a thickness of 1.6 mm (.+-.10%). In another
embodiment, a molded sample of the thermoplastic composition is
capable of achieving UL94 V0 rating at a thickness of 1.2 mm
(.+-.10%). In still another embodiment, a molded sample of the
thermoplastic composition is capable of achieving UL94 V0 rating at
a thickness of 1.0 mm (.+-.10%). In yet another embodiment, a
molded sample of the thermoplastic composition is capable of
achieving UL94 V0 rating at a thickness of 0.8 mm (.+-.10%).
[0077] The thermoplastic compositions of the present invention can
be formed using any known method of combining multiple components
to form a thermoplastic resin. In one embodiment, the components
are first blended in a high-speed mixer. Other low shear processes
including but not limited to hand mixing can also accomplish this
blending. The blend is then fed into the throat of a twin-screw
extruder via a hopper. Alternatively, one or more of the components
can be incorporated into the composition by feeding directly into
the extruder at the throat and/or downstream through a sidestuffer.
The extruder is generally operated at a temperature higher than
that necessary to cause the composition to flow. The extrudate is
immediately quenched in a water batch and pelletized. The pellets
so prepared when cutting the extrudate can be one-fourth inch long
or less as desired. Such pellets can be used for subsequent
molding, shaping, or forming.
[0078] Shaped, formed, or molded articles including the
thermoplastic compositions are also provided. The thermoplastic
compositions can be molded into useful shaped articles by a variety
of means such as injection molding, extrusion, rotational molding,
blow molding and thermoforming to form articles such as, for
example, personal computers, notebook and portable computers, cell
phone antennas and other such communications equipment, medical
applications, RFID applications, automotive applications, and the
like.
[0079] The present invention is further illustrated by the
following non-limiting examples.
EXAMPLES
[0080] In the first two examples, PC/ABS compounds (available from
SABIC Innovative Plastics) were tested using the same amount of
flame retaradent (BDADP--available from Nagase Co. Ltd.). The LDS
additive was copper chromium oxide spinel (available from Ferro Far
East Limited). The formulations also included other additives--TSAN
(from SABIC Innovative Plastics), mold release (PETS from Faci Asia
Pacific PTE LTD), antioxidant (Irganox1076 from Ciba), stabilizer
(IRGAFOS 168 from Ciba) and impact modifier (silicone-acrylic-based
impact modifier METABLEN S-2001 from Mitsubishi). For Sample A, the
composition included 0.64% TSAN, 0.53% mold release, 0.085%
antioxidant, 0.085% stabilizer and 4.25% impact modifier. For
Sample B, the composition included 0.35% TSAN, 0.5% mold release,
0.08% antioxidant, 0.08% stabilizer and 4% impact modifier.
[0081] The samples were tested for their flame out time (FOT),
which was measured according to UL 94 testing standards. In
addition, the probablity of first time pass ("p(ftp)", and measured
according to the methods set forth in US Patent No. 6,308,142) was
also determined, with higher probabilities showing better flame
retardant characteristics.
[0082] In the first sample, with 13.5 wt % BPADP, the flame out
time (FOT) of 5 bars (thickness: 0.8 mm) under aging condition was
111.8 seconds, with the flame time of at least 4 bars out of 10
bars tested exceeding 10 seconds. But when 5 wt % of copper
chromium oxide spinel was added, there were no bars that had a
flame time that exceeded 10 seconds, with the longest FOT of 4.2 s.
Furthermore, the FOT of 5 bars was only 17.3 seconds. That is to
say the addtion of copper chromium oxide spinel as the LDS additive
dramatically reduced the flame time, and therefore increased the
flame retardancy, of the compounds. According to UL94 V0
regulation, sample A (w/o copper chromium oxide spinel) failed to
pass V0 at 0.8 mm, while sample B (with 5 wt % copper chromium
oxide spinel) passed V0 at 0.8 mm. The results can be seen in Table
1.
TABLE-US-00001 TABLE 1 Formulation A B PC/ABS % 80.9 76.5 BPADP %
13.5 13.5 Copper chromium oxide spinel % 5 Others % 5.6 5 FR
property p(ftp) value 0.0002 0.99 FOT (5 bars) sec 111.8 17.3
[0083] In the next two examples, it was shown that in order to meet
UL94 requirement V0 at 0.8 mm, if no copper chromium oxide spinel
was added to the compounds, at least 16.5 wt % of BPADP was needed.
While if only 5 wt % copper chromium oxide spinel was added, 12.5
wt % of BPADP can pass, as shown in Table 2. Therefore, the LDS
additive unexpectedly helped increase the FR performance of the
compositions despite using lower amounts of FR, which enabled
higher HDT to be achieved. For these samples, the types and amounts
of the other additives is as follows--for Sample C, the composition
included 0.622% TSAN, 0.518% mold release, 0.0829% antioxidant,
0.0829% stabilizer and 3.145% impact modifier; for Sample D, the
composition included 0.606% TSAN, 0.505% mold release, 0.0808%
antioxidant, 0.0808% stabilizer and 4.23% impact modifier.
TABLE-US-00002 TABLE 2 Formulation C D PC/ABS % 79 77 BPADP % 16.5
12.5 Copper chromium oxide spinel % 5 Others % 4.5 5.5 FR property
p(ftp) value 0.86 0.86 FOT (5 bars) sec 41 32.3 HDT C 75.3 80.8
[0084] In the next set of examples, it was shown that in order to
meet UL94 requirement V0 at 0.8 mm, if 8.0 wt % or 20.0 wt % copper
chromium oxide spinel was added, 11.0 wt % or 10.0 wt % of BPADP
can pass, as shown in Table 3. Therefore, the LDS additive
unexpectedly helped increase the FR performance of the compositions
despite using lower amounts of FR, which enabled higher HDT to be
achieved. The results can be seen in Table 3. For these samples,
the types and amounts of the other additives is as follows--for
Sample E, the composition included 0.56% TSAN, 0.46% mold release,
0.07% antioxidant, 0.08% stabilizer and 3.05% impact modifier; for
Sample F, the composition included 0.62% TSAN, 0.52% mold release,
0.07% antioxidant, 0.08% stabilizer and 4.15% impact modifier.
TABLE-US-00003 TABLE 3 Formulation C E F PC/ABS % 79 76.8 64.5
BPADP % 16.5 11 10 Copper chromium oxide spinel % 8 20 Others % 4.5
4.2 5.5 FR property p(ftp) value 0.86 0.95 0.95 FOT (5 bars) sec 41
26.4 28.2 HDT C 75.3 82.2 86.5
[0085] In the next set of examples, a separate LDS additive was
used. In these examples, the LDS additive was copper hydroxide
phosphate from Sigma Alrich. To achieve UL performance level of V0
at 0.8 mm, 15.0 wt % of BPADP is enough with only 5.0 wt % copper
hydroxide phosphate in the compounds. As seen in Table 4, despite a
lower amount of FR agent (BDADP), better FR performance was
achieved through a lower flame out time and higher p(flp). For this
sample, the type and amount of the other additives is as
follows--for Sample G, the composition included 0.622% TSAN, 0.518%
mold release, 0.0829% antioxidant, 0.0829% stabilizer and 3.345%
impact modifier.
TABLE-US-00004 TABLE 4 Formulation C G PC/ABS % 79 75.8 BPADP %
16.5 15 Copper hydroxide phosphate % 5 Others % 4.5 4.7 FR property
p(ftp) value 0.86 0.99 FOT (5 bars) sec 41 27.1 HDT C 75.3 76.5
[0086] In the next set of examples, a different flame retardant was
used. In these examples, RDP from Supresta was used. With only 5.0
wt % copper chromium oxide spinel, V0 at 0.8 mm can be achieved
with 13.5 wt % RDP in the compounds other than 16.5 wt % RDP.
Again, as can be seen, lower amounts of RDP, when used in
conjunction with the LDS additive unexpectedly resulted in
comparable FR performance and higher HDT. These results can be seen
in Table 5. For these samples, the types and amounts of the other
additives is as follows--for Sample H, the composition included
0.622% TSAN, 0.521% mold release, 0.083% antioxidant, 0.083%
stabilizer and 3.6% impact modifier; for Sample I, the composition
included 0.622% TSAN, 0.521% mold release, 0.083% antioxidant,
0.083% stabilizer and 3.5% impact modifier.
TABLE-US-00005 TABLE 5 Formulation H I PC/ABS % 78.6 76.7 RDP %
16.5 13.5 Copper chromium oxide spinel % 5 Others % 4.9 4.8 FR
property p(ftp) value 0.87 0.9 FOT (5 bars) sec 24.3 26.1 HDT C
68.3 73.3
[0087] In the next set of examples, 10.0wt % copper chromium oxide
spinel was added to PPO/RDP compounds to show that the effects
previously shown are not limited to PC/ABS blends. The PPO came
from SABIC Innovative Plastics. In these examples, it is seen that,
again, lower amounts of RDP resulted in better FR performance when
combined with the LDS additive. The results can be seen in Table 6.
For these samples, the types and amounts of the other additives is
as follows--for Sample J, the composition included 0.242% TSAN,
0.705% mold release, and 0.403% antioxidant; for Sample K, the
composition included 0.228% TSAN, 0.665% mold release, and 0.38%
antioxidant.
TABLE-US-00006 TABLE 6 Formulation J K PPO % 83.4 78.7 RDP % 15.2
10 Copper chromium oxide spinel % 10 Others % 1.4 1.3 FR property
p(ftp) value 0.92 0.99 FOT (5 bars) sec 32.1 28.6
[0088] While typical embodiments have been set forth for the
purpose of illustration, the foregoing descriptions should not be
deemed to be a limitation on the scope of the invention.
Accordingly, various modifications, adaptations, and alternatives
can occur to one skilled in the art without departing from the
spirit and scope of the present invention.
* * * * *